Shynthesis of Carbocyclic Nucleosides Having Biological Function

1.考察了顺-3，5-二取代环戊烯的顺式二羟基化反应，得到碳环核苷。它的立体选择性与环戊烯取代基的构象有关。将分子氟与双环[2.2.1]HEPT-2-烯的衍生物进行了加成反应，并转化为含氟碳环核苷。这些核苷的生物学评价没有显示出任何抗HIV活性。研究了苯磺酰氰化物与环戊二烯在手性Lewis酸催化下的不对称Diels-Alder反应，得到了光学活性的手性碳环核苷合成子2-氮杂二环[2.2.1]HEPT-5-en-3-one。冰片二烯或双环酰胺与亚硝酮生成的环硝酮发生1，3-偶极环加成反应，得到立体选择性的外环加合物，可作为合成含α-氨基酸残基的碳环核苷的中间体。合成了一种新的双烯亲和剂--三氟乙酰氨基甲基马来酸二甲酯。亲双烯分子很容易与环戊二烯反应生成碳环高核苷的双环化合物。用腺苷脱氨酶在高压下对碳环腺嘌呤核苷进行脱氨基反应，结果表明该脱氨基反应是外消旋碳环腺嘌呤核苷拆分的有效步骤。

1. The cis-dihydroxylation of cis-3,5-disubstituted cyclopentenes leading to carbocyclic nucleosides was examined. Its stereoselectivity was found to be attibutable to the conformation of substituents of cyclopentenes.2. Addition of molecular fluorine to bicyclo [2.2.1] hept-2-ene derivatives and conversion to fluorine-containing carbocyclic nucleosides were carried out. Biological evaluation of these nucleosides did not show any anti-HIV activity.3. Asymmetric hetero Diels-Alder reaction of benzenesulfonyl cyanide with cyclopentadiene using chiral Lewis acids was investigated to give opticaliy active 2-azabicyclo [2.2.1] hept-5-en-3-one, which was a synthon of chiral carbocyclic nucleosides.4. The 1,3-dipolar cycloaddition reaction of bornadiene or bicycloamides with cyclic nitrones obtained from nitrosoketene with ketones gave stereoselectively the exocycloadducts, which would be intermediates for the synthesis of carbocyclic nucleosides containing an alpha-amino acid residue.5. A new dienophile, dimethyl trifluoroacetylaminomethylenemalonate, was created. The dienophile reacted readily with cyclopentadiene to give a bicyclic compound leading to carbocyclic homo-nucleosides.6. Deamination of carbocyclic adenine nucleosides by adenosine deaminase under highpressure revealed that the deamination was a useful procedure for the kinetical resolution of racemic carbocyclic nucleosides.